Matting agent composition containing polytrimethylene ether diol and use thereof

ABSTRACT

The present invention is directed to a matting agent for reducing gloss of a coating. The matting agent comprises: a) a silica component; b) a polytrimethylene ether diol; c) one or more solvents; and d) optionally, one or more polymers. This invention is further directed to a matting agent comprising components derived from renewable resources.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority under 35 U.S.C. §119 from U.S.Provisional Application Ser. No. 61/174,070 (filed Apr. 30, 2009), thedisclosure of which is incorporated by reference herein for all purposesas if fully set forth.

FIELD OF INVENTION

The present invention is directed to a matting agent for reducing glossof a coating. This invention is further directed to a matting agentcomprising components derived from renewable resources. This inventionis further directed to a method for using the matting agent.

BACKGROUND OF INVENTION

Consumers' and industrial desires on coating appearance are diversified.Sometimes, a preference is given to coatings having low gloss or lowluster. These desires present challenges to coating industry forproducing coatings that have varied appearances including low gloss orlow luster with reduced shining, reflecting light, glitter, sparkle orsheen. Typically, such coatings with low gloss are produced byincorporating a matting agent that imparting matting effect. The mattingagent can be inorganic particles, such as silicon compound particles.However, with the addition of such inorganic particles, coatings becomebrittle and less flexible that could result in less resistance toabrasion, chipping, cracking, or low adhesion.

Therefore, continued needs arise for improved matting agent.

STATEMENT OF INVENTION

This invention is directed to a matting agent comprising:

-   -   a) a silica component,    -   b) a polytrimethylene ether diol having a Mn (number average        molecular weight) in a range of from 500 to 10,000; and    -   c) one or more solvents.

The matting agent can further comprise one or more polymers selectedfrom acrylic polymer, polyester polymer, or a combination thereof.

This invention is also directed to a method for reducing gloss of a drycoating layer on a substrate, said coating layer is formed from acoating composition, said method comprising the steps of:

-   -   i) providing a matting agent comprising:        -   a) a silica component;        -   b) a polytrimethylene ether diol having a Mn (number average            molecular weight) in a range of from 500 to 10,000;        -   c) one or more solvents; and        -   d) one or more polymers selected from acrylic polymer,            polyester polymer, or a combination thereof;    -   ii) mixing said matting agent with said coating composition to        form a matt coating mix;    -   iii) applying said matt coating mix over said substrate to form        a wet coating layer; and    -   iv) curing said wet coating layer to form said dry coating        layer.

DETAILED DESCRIPTION

The features and advantages of the present invention will be morereadily understood, by those of ordinary skill in the art, from readingthe following detailed description. It is to be appreciated that certainfeatures of the invention, which are, for clarity, described above andbelow in the context of separate embodiments, may also be provided incombination in a single embodiment. Conversely, various features of theinvention that are, for brevity, described in the context of a singleembodiment, may also be provided separately or in any sub-combination.In addition, references in the singular may also include the plural (forexample, “a” and “an” may refer to one, or one or more) unless thecontext specifically states otherwise.

The use of numerical values in the various ranges specified in thisapplication, unless expressly indicated otherwise, are stated asapproximations as though the minimum and maximum values within thestated ranges were both proceeded by the word “about.” In this manner,slight variations above and below the stated ranges can be used toachieve substantially the same results as values within the ranges.Also, the disclosure of these ranges is intended as a continuous rangeincluding every value between the minimum and maximum values.

As used herein:

“Gloss” means surface gloss of a coating surface and is related to theamount of incident light that is reflected at the specular reflectanceangle of the mean of that surface. Gloss can be measured with a specularglossmeter, such as those available from Byk-Gardener, Geretsried,Germany.

“DOI” (Distinctness of Image) is a quantitative measure of coatingappearance that measures the light reflected at and around the specularreflectance angle. It can be determined according to the methoddescribed in ASTM D 5767. DOI can be measured with wave scaninstruments, such as those available from Byk-Gardener, Geretsried,Germany. DOI measures not only the amount of incident light that isreflected at the specular reflectance angle, but also the distributionof the reflected light around the reflectance specular angle, typically+/−0.3° from the specular angle. A coating surface that gives fuzzy ordistorted image generally produces lower DOI reading. A coatingreflecting 100% of lights at the specular angle gives a DOI reading of100.

The term “(meth)acrylate” means methacrylate or acrylate.

The term “two-pack coating composition” or “2K coating composition”refers to a coating composition having two packages that are stored inseparate containers and sealed to increase the shelf life of the coatingcomposition during storage. The two packages are mixed just prior to useto form a pot mix, which has a limited pot life, typically ranging froma few minutes (15 minutes to 45 minutes) to a few hours (4 hours to 8hours). The pot mix is then applied as a layer of a desired thickness ona substrate surface, such as an automobile body. After application, thelayer dries and cures at ambient or at elevated temperatures to form acoating on the substrate surface having desired coating properties, suchas, adhesion, gloss, and DOI.

The term “one-pack coating composition” or “1K coating composition”refers to a coating composition having one package that can be storedfor a certain shelf life. For example, a 1K coating composition can be aUV mono-cure coating composition that can be prepared to form a pot mixand stored in a sealed container. As long as the UV mono-cure coatingcomposition is not exposed to UV radiation, the UV mono-cure coatingcomposition can have indefinite pot life. Other examples of 1K coatingcomposition can include 1K coating compositions having blockedcrosslinking agent such as blocked isocyanates, moisture curing 1Kcoating compositions, oxygen curing 1K coating compositions, or heatcuring 1K coating compositions as known in coating industry.

The term “crosslinkable component” refers to a component having“crosslinkable functional groups” that are functional groups positionedin each molecule of the compounds, oligomer, polymer, the backbone ofthe polymer, pendant from the backbone of the polymer, terminallypositioned on the backbone of the polymer, or a combination thereof,wherein these functional groups are capable of crosslinking withcrosslinking functional groups (during the curing step) to produce acoating in the form of crosslinked structures. One of ordinary skill inthe art would recognize that certain crosslinkable functional groupcombinations would be excluded, since, if present, these combinationswould crosslink among themselves (self-crosslink), thereby destroyingtheir ability to crosslink with the crosslinking functional groups. Aworkable combination of crosslinkable functional groups refers to thecombinations of crosslinkable functional groups that can be used incoating applications excluding those combinations that wouldself-crosslink.

Typical crosslinkable functional groups can include hydroxyl, thiol,isocyanate, thioisocyanate, acetoacetoxy, carboxyl, primary amine,secondary amine, epoxy, anhydride, ketimine, aldimine, or a workablecombination thereof. Some other functional groups such as orthoester,orthocarbonate, or cyclic amide that can generate hydroxyl or aminegroups once the ring structure is opened can also be suitable ascrosslinkable functional groups.

The term “crosslinking component” refers to a component having“crosslinking functional groups” that are functional groups positionedin each molecule of the compounds, oligomer, polymer, the backbone ofthe polymer, pendant from the backbone of the polymer, terminallypositioned on the backbone of the polymer, or a combination thereof,wherein these functional groups are capable of crosslinking with thecrosslinkable functional groups (during the curing step) to produce acoating in the form of crosslinked structures. One of ordinary skill inthe art would recognize that certain crosslinking functional groupcombinations would be excluded, since, if present, these combinationswould crosslink among themselves (self-crosslink), thereby destroyingtheir ability to crosslink with the crosslinkable functional groups. Aworkable combination of crosslinking functional groups refers to thecombinations of crosslinking functional groups that can be used incoating applications excluding those combinations that wouldself-crosslink. One of ordinary skill in the art would recognize thatcertain combinations of crosslinking functional group and crosslinkablefunctional groups would be excluded, since they would fail to crosslinkand produce the film forming crosslinked structures. The crosslinkingcomponent can comprise one or more crosslinking agents that have thecrosslinking functional groups.

Typical crosslinking functional groups can include hydroxyl, thiol,isocyanate, thioisocyanate, acetoacetoxy, carboxyl, primary amine,secondary amine, epoxy, anhydride, ketimine, aldimine, orthoester,orthocarbonate, cyclic amide or a workable combination thereof.

The term “matting agent” refers to a composition that can be used tomatt a glossy surface or reduce the gloss of surface. A matting agentcan be used to reduce or control gloss of coatings.

This invention is directed to a matting agent that can comprise:

-   -   a) a silica component,    -   b) a polytrimethylene ether diol having a Mn (number average        molecular weight) in a range of from 500 to 10,000; and    -   c) one or more solvents.

The matting agent can further comprise:

-   -   d) one or more polymers selected from acrylic polymer, polyester        polymer, or a combination thereof.

In one embodiment, the matting agent can consist of:

-   -   a) a silica component,    -   b) a polytrimethylene ether diol having a Mn (number average        molecular weight) in a range of from 500 to 10,000;    -   c) one or more solvents; and    -   d) one or more polymers selected from acrylic polymer, polyester        polymer, or a combination thereof.

In another embodiment, the matting agent can consist essentially of:

-   -   a) a silica component,    -   b) a polytrimethylene ether diol having a Mn (number average        molecular weight) in a range of from 500 to 10,000;    -   c) one or more solvents; and    -   d) one or more polymers selected from acrylic polymer, polyester        polymer, or a combination thereof.

The matting agent can contain trace amounts of impurities that may bepresent in any or all of the silica, the polytrimethylene ether diol,the solvent, or the polymers.

The silica component can comprise silica particles having an averageparticle size in a range of from 2 to 20 micrometers (μm). In oneexample, the silica particles have an average particle size in a rangeof from 2 to 20 micrometers (μm), in another example, in a range of from2 to 10 micrometers (μm), in yet another example in a range of from 2 to8 micrometers (μm). In yet another example, the silica component canconsist of silica particles having an average particle size in a rangeof from 2 to 20 micrometers (μm).

The silica particles can have different surface treatment. In oneexample, the silica particles are organic surface treated silicaparticles. In another example, silica particles are untreated. In yetanother example, the silica particles are thermally treated. Silicaparticles having hydrophobic surface property can be preferred.

Commercial available silica particles, such those available under thetrademark ACEMATT® from marketed Degussa Evonik, can be suitable forthis invention. Silica particles that have organic surface-treatment,such as ACEMATT® OK 412 can be preferred.

The polytrimethylene ether dial suitable for the coating composition ofthis disclosure can have a number average molecular weight (Mn) in therange of from 500 to 10,000, preferably 500 to 8,000, even preferably500 to 4,000. The polytrimethylene ether diol has a Tg of about −75° C.,a polydispersity in the range of from 1.1 to 2.1 and a hydroxyl numberin the range of from 20 to 200.

Suitable polytrimethylene ether diol can be prepared by anacid-catalyzed polycondensation of 1,3-propanediol, such as described inU.S. Pat. Nos. 6,977,291 and 6,720,459. The polytrimethylene ether diolcan also be prepared by a ring opening polymerization of a cyclic ether,oxetane, such as described in J. Polymer Sci., Polymer Chemistry Ed. 28,449 to 444 (1985). The polycondensation of 1,3-propanediol is preferredover the use of oxetane since the diol is a less hazardous, stable, lowcost, commercially available material and can be prepared by use ofpetro chemical feed-stocks or renewable resources.

A bio-route via fermentation of a renewable resource can be used toobtain the 1,3-propanediol. One example of renewable resources is cornsince it is readily available and has a high rate of conversion to1,3-propanediol and can be genetically modified to improve yields to the1,3-propanediol. Examples of typical bio-route can include thosedescribed in U.S. Pat. No. 5,686,276, U.S. Pat. No. 5,633,362 and U.S.Pat. No. 5,821,092.

Copolymers of polytrimethylene ether diol also can be suitable for thecoating composition of this disclosure. Examples of such suitablecopolymers of polytrimethylene ether diol can be prepared bycopolymerizing 1,3-propanediol with another diol, such as, ethane diol,hexane diol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol,trimethylol propane and pentaerythritol. In one example, the copolymersof polytrimethylene ether diol can be polymerized from monomers have1,3-propanediol in a range of from 50% to 99%. In another example, thecopolymers of polytrimethylene ether diol can be polymerized frommonomers have 1,3-propanediol in a range of from 60% to 99%. In yetanother example, the copolymers of polytrimethylene ether dial can bepolymerized from monomers have 1,3-propanediol in a range of from 70% to99%.

A blend of a high and a low molecular weight polytrimethylene ether diolcan be used. In one example, the high molecular weight polytrimethyleneether diol can have an Mn in a range of from 1,000 to 4,000 and the lowmolecular weight polytrimethylene ether diol can have an Mn in a rangeof from 150 to 500. The average Mn of the blended polytrimethylene etherdiol can be in a range of from 500 to 4,000. In another example, thehigh molecular weight polytrimethylene ether diol can have an Mn in arange of from 1,000 to 4,000 and the low molecular weightpolytrimethylene ether diol can have an Mn in a range of from 150 to 500and the average Mn of the blend can be in a range of from 500 to 3,000.

Blends of the polytrimethylene ether diol and other cycloaliphatichydroxyl containing either branched or linear oligomers can be used.Such hydroxyl containing oligomers are known to those skilled in theart. Examples of such hydroxyl containing oligomers can include thosedisclosed by Barsotti, et al. in U.S. Pat. No. 6,221,494.

Polymers that are suitable for this invention can include linear orbranched acrylic polymers, linear or branched polyesters, linear orbranched acrylic polymers having hydroxyl functional groups, linear orbranched hydroxyl polyesters having hydroxyl functional groups, or acombination thereof.

The acrylic polymer used in the composition can have a weight averagemolecular weight (Mw) of about 5,000 to 100,000, and a glass transitiontemperature (Tg) in a range of from −40° C. to 80° C. and containfunctional groups or pendant moieties that are reactive with isocyanateor other crosslinking functional groups, such as, for example, hydroxyl,amino, amide, glycidyl, silane and carboxyl groups. These acrylicpolymers can be straight chain polymers (also known as linear acrylicpolymers), branched polymers, block copolymers, graft polymers, or othertypes of acrylic polymers.

The acrylic polymers can be polymerized from a plurality of monomers,such as acrylates, methacrylates or derivatives thereof, as known tothose skilled in the art.

Suitable monomers can include linear alkyl(meth)acrylates having 1 to 12carbon atoms in the alkyl group, cyclic or branched alkyl(meth)acrylateshaving 3 to 12 carbon atoms in the alkyl group, includingisobornyl(meth)acrylate, styrene, alpha methyl styrene, vinyl toluene,(meth)acrylonitrile, (meth)acryl amides and monomers that providecrosslinkable functional groups, such as, hydroxy alkyl(meth)acrylateshaving 1 to 4 carbon atoms in the alkyl group, glycidyl(meth)acrylate,amino alkyl(meth)acrylates having 1 to 4 carbon atoms in the alkylgroup, (meth)acrylic acid, and alkoxy silyl alkyl(meth)acrylates, suchas, trimethoxysilylpropyl(meth)acrylate.

Suitable monomers can also include, for example, hydroxyalkyl esters ofalpha,beta-olefinically unsaturated monocarboxylic acids with primary orsecondary hydroxyl groups. These may, for example, comprise thehydroxyalkyl esters of acrylic acid, methacrylic acid, crotonic acidand/or isocrotonic acid. Examples of suitable hydroxyalkyl esters ofalpha,beta-olefinically unsaturated monocarboxylic acids with primaryhydroxyl groups can include hydroxyethyl(meth)acrylate,hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate,hydroxyamyl(meth)acrylate, hydroxyhexyl(meth)acrylate. Examples ofsuitable hydroxyalkyl esters with secondary hydroxyl groups can include2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate,3-hydroxybutyl(meth)acrylate.

Suitable monomers can also include monomers that are reaction productsof alpha,beta-unsaturated monocarboxylic acids with glycidyl esters ofsaturated monocarboxylic acids branched in alpha position, for examplewith glycidyl esters of saturated alpha-alkylalkanemonocarboxylic acidsor alpha,alpha′-dialkylalkanemonocarboxylic acids. These can comprisethe reaction products of (meth)acrylic acid with glycidyl esters ofsaturated alpha,alpha-dialkylalkanemonocarboxylic acids with 7 to 13carbon atoms per molecule, particularly preferably with 9 to 11 carbonatoms per molecule. These reaction products can be formed before, duringor after copolymerization reaction of the acrylic polymer.

Suitable monomers can further include monomers that are reactionproducts of hydroxyalkyl(meth)acrylates with lactones.Hydroxyalkyl(meth)acrylates which can be used include.

Suitable monomers can also include unsaturated monomers such as, forexample, allyl glycidyl ether, 3,4-epoxy-1-vinylcyclohexane,epoxycyclohexyl(meth)acrylate, vinyl glycidyl ether andglycidyl(meth)acrylate, that can be used to provide the acrylic polymerwith glycidyl groups.

Suitable monomers can also include monomers that are free-radicallypolymerizable, olefinically unsaturated monomers which, apart from atleast one olefinic double bond, do not contain additional functionalgroups. Such monomers include, for example, esters of olefinicallyunsaturated carboxylic acids with aliphatic monohydric branched orunbranched as well as cyclic alcohols with 1 to 20 carbon atoms.Examples of the unsaturated carboxylic acids can include acrylic acid,methacrylic acid, crotonic acid and isocrotonic acid. In one embodiment,esters of (meth)acrylic acid can be used. Examples of esters of(meth)acrylic acid can include methyl acrylate, ethyl acrylate,isopropyl acrylate, tert.-butyl acrylate, n-butyl acrylate, isobutylacrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate andthe corresponding methacrylates. Examples of esters of (meth)acrylicacid with cyclic alcohols can include cyclohexyl acrylate,trimethylcyclohexyl acrylate, 4-tert-butylcyclohexyl acrylate, isobornylacrylate and the corresponding methacrylates.

Suitable monomers can also include unsaturated monomers that do notcontain additional functional groups for example, vinyl ethers, such as,isobutyl vinyl ether and vinyl esters, such as, vinyl acetate, vinylpropionate, vinyl aromatic hydrocarbons, preferably those with 8 to 9carbon atoms per molecule. Examples of such monomers can includestyrene, alpha-methylstyrene, chlorostyrenes, 2,5-dimethylstyrene,p-methoxystyrene, vinyl toluene. In one embodiment, styrene can be used.

Suitable monomers can also include small proportions of olefinicallypolyunsaturated monomers. These olefinically polyunsaturated monomersare monomers having at least 2 free-radically polymerizable double bondsper molecule. Examples of these olefinically polyunsaturated monomerscan include divinylbenzene, 1,4-butanediol diacrylate, 1,6-hexanedioldiacrylate, neopentyl glycol dimethacrylate, and glyceroldimethacrylate.

The acrylic polymers of this disclosure can generally be polymerized byfree-radical copolymerization using conventional processes well known tothose skilled in the art, for example, bulk, solution or beadpolymerization, in particular by free-radical solution polymerizationusing free-radical initiators.

The acrylic polymer can contain (meth)acrylamides. Typical examples ofsuch acrylic polymers can be polymerized from monomers including(meth)acrylamide. In one example, such acrylic polymer can bepolymerized from (meth)acrylamide and alkyl(meth)acrylates, hydroxyalkyl(meth)acrylates, (meth)acrylic acid and one of the aforementionedolefinically unsaturated monomers.

The polyester suitable for this invention can be linear polyestershaving one or more crosslinkable functional groups and having a glasstransition temperature (Tg) in a range of from −75° C. to 80° C. Typicalsuitable linear polyesters can have a hydroxyl number in a range of from5 to 250. Typical suitable linear polyester can have a weight averagemolecular weight in a range of from 1,000 to 40,000. The weight averagemolecular weight can be in a range of from 1,000 to 40,000 in oneembodiment, 1,000 to 20,000 in another embodiment, 1,000 to 10,000 inyet another embodiment. The polyesters may be saturated or unsaturatedand optionally, may be modified with fatty acids. These polyesters canbe the esterification product of one or more polyhydric alcohols, suchas, alkylene diols and glycols; and carboxylic acids such asmonocarboxylic acids, polycarboxylic acids or anhydrides thereof, suchas, dicarboxylic and/or tricarboxylic acids or tricarboxylic acidanhydrides.

One example of suitable linear polyester can be the estrificationproduct of neopentyl glycol, isophthalic acid, adipic acid,pentaerythritol and anhydride.

The polyester can also be highly branched copolyesters. The highlybranched copolyester can have a hydroxyl number in a range of from 5 to200 and can have a weight average molecular weight in a range of from1,000 to 50,000. The weight average molecular weight can be in a rangeof from 1,000 to 50,000 in one embodiment, 1,000 to 40,000 in anotherembodiment, 1,500 to 40,000 in yet another embodiment, 1,500 to 30,000in yet another embodiment, and 2,000 to 30,000 in further anotherembodiment. The highly branched copolyester can have one or morehydroxyl crosslinkable function groups.

The highly branched copolyester can be conventionally polymerized from amonomer mixture containing a dual functional monomer selected from thegroup consisting of a hydroxy carboxylic acid, a lactone of a hydroxycarboxylic acid and a combination thereof; and one or more hyperbranching monomers.

One example of a highly branched polyester suitable for this inventioncan be synthesized by reacting dimethylol propionic acid,pentaerythritol, and caprolactone.

Conventional methods for synthesizing polyesters are known to thoseskilled in the art. Examples of the conventional methods can includethose described in U.S. Pat. No. 5,270,362 and U.S. Pat. No. 6,998,154.

The matting agent of this invention can comprise one or more solvents.Any typical organic solvents commonly used in coating industry can besuitable for this invention. Examples of solvents can include, but notlimited to, aromatic hydrocarbons, such as, toluene, xylene; ketones,such as, acetone, methyl ethyl ketone, methyl isobutyl ketone, methylamyl ketone and diisobutyl ketone; esters, such as, ethyl acetate,n-butyl acetate, isobutyl acetate and a combination thereof. Somecommercial available solvents, such as Oxsol® 100 available from MANA,New York, N.Y., USA, under respective registered trademark, can also beused.

The matting agent of this invention can be mixed with a coatingcomposition to form a matt coating mix for producing a coating withreduced gloss. One advantage of the matting agent of this invention isthat the matting agent can be mixed with a broad range of solvent basedcoating compositions. The coating compositions can include any solventborne 1K or 2K coating compositions. The coating compositions can alsoinclude dual cure coating compositions, such as those can be cured byboth UV and crosslinking agent. Most commercially available 1K, 2K ordual cure coating compositions can be suitable for use with the mattingagent of this invention. A coating composition having hydroxylcrosslinkable functional groups is preferred.

The coating compositions can include a crosslinking component comprisingcompounds having crosslinking functional groups. Examples of suchcompounds can be organic polyisocyanates. Examples of organicpolyisocyanates include aliphatic polyisocyanates, cycloaliphaticpolyisocyanates, aromatic polyisocyanates and isocyanate adducts. Anyisocyanate suitable for coating can be used.

Examples of suitable aliphatic, cycloaliphatic and aromaticpolyisocyanates that can be used include the following: 2,4-toluenediisocyanate, 2,6-toluene diisocyanate (“TDI”), 4,4-diphenylmethanediisocyanate (“MDI”), 4,4′-dicyclohexyl methane diisocyanate (“H12MDI”),3,3′-dimethyl-4,4′-biphenyl diisocyanate (“TODI”), 1,4-benzenediisocyanate, trans-cyclohexane-1,4-diisocyanate, 1,5-naphthalenediisocyanate (“NDI”), 1,6-hexamethylene diisocyanate (“HDI”), 4,6-xylenediisocyanate, isophorone diisocyanate, (“IPDI”), other aliphatic orcycloaliphatic di-, tri- or tetra-isocyanates, such as, 1,2-propylenediisocyanate, tetramethylene diisocyanate, 2,3-butylene diisocyanate,octamethylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate,dodecamethylene diisocyanate, omega-dipropyl ether diisocyanate,1,3-cyclopentane diisocyanate, 1,2-cyclohexane diisocyanate,1,4-cyclohexane diisocyanate, 4-methyl-1,3-diisocyanatocyclohexane,dicyclohexylmethane-4,4′-diisocyanate, 3,3′-dimethyl-dicyclohexylmethane4,4′-diisocyanate, polyisocyanates having isocyanurate structural units,such as, the isocyanurate of hexamethylene diisocyanate and theisocyanurate of isophorone diisocyanate, the adduct of 2 molecules of adiisocyanate, such as, hexamethylene diisocyanate, uretidiones ofhexamethylene diisocyanate, uretidiones of isophorone diisocyanate and adiol, such as, ethylene glycol, the adduct of 3 molecules ofhexamethylene diisocyanate and 1 molecule of water, allophanates,trimers and biurets, for example, of hexamethylene diisocyanate,allophanates, trimers and biurets, for example, of isophoronediisocyanate and the isocyanurate of hexane diisocyanate. MDI, HDI, TDIand isophorone diisocyanate are preferred because of their commercialavailability.

Tri-functional isocyanates also can be used, such as, triphenyl methanetriisocyanate, 1,3,5-benzene triisocyanate, 2,4,6-toluene triisocyanate.Trimers of diisocyanates, such as, the trimer of hexamethylenediisocyanate, sold as Tolonate® HDT from Rhodia Corporation and thetrimer of isophorone diisocyanate are also suitable.

An isocyanate functional adduct can be used, such as, an adduct of analiphatic polyisocyanate and a polyol or an adduct of an aliphaticpolyisocyanate and an amine. Also, any of the aforementionedpolyisocyanates can be used with a polyol to form an adduct. Polyols,such as, trimethylol alkanes, particularly, trimethylol propane orethane can be used to form an adduct.

Depending upon the type of crosslinking agent, the coating compositionof this invention can be formulated as one-pack (1K) or two-pack (2K)coating composition. If polyisocyanates with free isocyanate groups areused as the crosslinking agent, the coating composition can beformulated as a two-pack coating composition in that the crosslinkingagent is mixed with other components of the coating composition onlyshortly before mixing with the matting agent of this invention. Ifblocked polyisocyanates are, for example, used as the crosslinkingagent, the coating compositions can be formulated as a one-pack (1K)coating composition.

Typically, the coating composition can also include a catalyst to reducecuring time and to allow curing of the coating composition at ambienttemperatures. The ambient temperatures are typically referred to astemperatures in a range of from 18° C. to 35° C. Typical catalystsinclude organic metal salts, such as, dibutyl tin dilaurate, dibutyl tindiacetate, dibutyl tin dichloride, dibutyl tin dibromide, zincnaphthenate; compounds containing tertiary amino groups, such as,triethylamine; triphenyl boron, tetraisopropyl titanate, triethanolaminetitanate chelate, dibutyl tin dioxide, dibutyl tin dioctoate, tinoctoate, aluminum titanate, aluminum chelates, zirconium chelate,hydrocarbon phosphonium halides, such as, ethyl triphenyl phosphoniumiodide and other such phosphonium salts, and other catalysts or mixturesthereof known to those skilled in the art.

The coating composition can comprise one or more solvents. Examples ofsolvents can include, but not limited to, aromatic hydrocarbons, suchas, toluene, xylene; ketones, such as, acetone, methyl ethyl ketone,methyl isobutyl ketone, methyl amyl ketone and diisobutyl ketone;esters, such as, ethyl acetate, n-butyl acetate, isobutyl acetate and acombination thereof.

Typically, the coating composition can contain conventional inorganicand organic colored pigments, metallic flakes and powders, such as,aluminum flake and aluminum powders; special effects pigments, such as,coated mica flakes, coated aluminum flakes colored pigments, or acombination thereof can be used.

The coating composition can also comprise one or more ultraviolet lightstabilizers. Examples of such ultraviolet light stabilizers can includeultraviolet light absorbers, screeners, quenchers, and hindered aminelight stabilizers. An antioxidant can also be added to the coatingcomposition.

Typical ultraviolet light stabilizers can include benzophenones,triazoles, triazines, benzoates, hindered amines and mixtures thereof. Ablend of hindered amine light stabilizers, such as Tinuvin® 328 andTinuvin®123, all commercially available from Ciba Specialty Chemicals,Tarrytown, N.Y., under respective registered trademark, can be used.

Typical ultraviolet light absorbers can include hydroxyphenylbenzotriazoles, such as, 2-(2-hydroxy-5-methylphenyl)-2H-benzotrazole,2-(2-hydroxy-3,5-di-tert.amyl-phenyl)-2H-benzotriazole,2[2-hydroxy-3,5-di(1,1-dimethylbenzyl)phenyl]-2H-benzotriazole, reactionproduct of 2-(2-hydroxy-3-tert.butyl-5-methylpropionate)-2H-benzotriazole and polyethylene ether glycol having aweight average molecular weight of 300,2-(2-hydroxy-3-tert.butyl-5-iso-octyl propionate)-2H-benzotriazole;hydroxyphenyl s-triazines, such as,2-[4((2,-hydroxy-3-dodecyloxy/tridecyloxypropyl)-oxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[4(2-hydroxy-3-(2-ethylhexyl)-oxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)1,3,5-triazine,2-(4-octyloxy-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;hydroxybenzophenone U.V. absorbers, such as, 2,4-dihydroxybenzophenone,2-hydroxy-4-octyloxybenzophenone, and2-hydroxy-4-dodecyloxybenzophenone.

Typical hindered amine light stabilizers can includeN-(1,2,2,6,6-pentamethyl-4-piperidinyl)-2-dodecyl succinimide, N(1acetyl-2,2,6,6-tetramethyl-4-piperidinyl)-2-dodecyl succinimide,N-(2hydroxyethyl)-2,6,6,6-tetramethylpiperidine-4-ol-succinic acidcopolymer, 1,3,5 triazine-2,4,6-triamine,N,N′″[1,2-ethanediybis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]imino]-3,1-propanediyl]]bis[N,N′″-dibutyl-N′,N′″-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)],poly-[[6-[1,1,3,3-tetramethylbutyl)-amino]-1,3,5-trianzine-2,4-diyl][2,2,6,6-tetramethylpiperidinyl)-imino]-1,6-hexane-diyl[(2,2,6,6-tetramethyl-4-piperidinyl)-imino]),bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[3,5bis(1,1-dimethylethyl-4-hydroxy-phenyl)methyl]butylpropanedioate,8-acetyl-3-dodecyl-7,7,9,9,-tetramethyl-1,3,8-triazaspiro(4,5)decane-2,4-dione,and dodecyl/tetradecyl-3-(2,2,4,4-tetramethyl-2I-oxo-7-oxa-3,20-diazaldispiro(5.1.11.2)henicosan-20-yl)propionate.

Typical antioxidants can includetetrakis[methylene(3,5-di-tert-butylhydroxy hydrocinnamate)]methane,octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate,tris(2,4-di-tert-butylphenyl) phosphite,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trioneand benzenepropanoic acid, 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-C7-C9branched alkyl esters. Typically useful antioxidants can also includehydroperoxide decomposers, such as Sanko® HCA(9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide), triphenyl phosphateand other organo-phosphorous compounds, such as, Irgafos® TNPP from CibaSpecialty Chemicals, Irgafos® 168, from Ciba Specialty Chemicals,Ultranox® 626 from GE Specialty Chemicals, Mark PEP-6 from Asahi Denka,Mark HP-10 from Asahi Denka, Irgafos® P-EPQ from Ciba SpecialtyChemicals, Ethanox 398 from Albemarle, Weston 618 from GE SpecialtyChemicals, Irgafos® 12 from Ciba Specialty Chemicals, Irgafos® 38 fromCiba Specialty Chemicals, Ultranox® 641 from GE Specialty Chemicals andDoverphos® S-9228 from Dover Chemicals.

The coating compositions can comprise conventional coating additives.Examples of such additives can include wetting agents, leveling and flowcontrol agents, for example, Resiflow®S (polybutylacrylate), BYK® 320and 325 (high molecular weight polyacrylates), BYK® 347(polyether-modified siloxane) under respective registered trademarks,leveling agents based on (meth)acrylic homopolymers; rheological controlagents; thickeners, such as partially crosslinked polycarboxylic acid orpolyurethanes; and antifoaming agents. The additives can be used inconventional amounts familiar to those skilled in the art.

The matt coating mix produced by mixing the matting agent and a coatingcomposition can be suitable for use as vehicle or industrial coatingsfor producing a coating with certain properties, such as reduced gloss.The matt coating mix and can be applied using known processes, such asspraying, electrostatic spraying, dipping, brushing, rolling, or flowcoating. In the context of vehicle coating, the coating composition canbe used both for vehicle original equipment manufacturing (OEM) coatingand for repairing or refinishing coatings of vehicles and vehicle parts.Curing of the coating composition can be accomplished at ambienttemperatures, such as temperatures in a range of from 18° C. to 35° C.,or at elevated temperatures, such as at temperatures in a range of from35° C. to 150° C. Typical curing temperatures of 20° C. to 80° C., inparticular of 20° C. to 60° C., can be used.

The use of polytrimethylene ether diol in coating compositions has beendescribed in U.S. Pat. Nos. 6,875,514 and 7,169,475. Thepolytrimethylene ether diol is believed to provide improved flexibilityto a coating therefore improving chip resistance.

Applicants unexpectedly discovered that adding polytrimethylene etherdial into a matting composition can provide matting effect to a coating.Applicants further unexpectedly discovered that the use ofpolytrimethylene ether dial improves matting effect of silica particles.Coatings produced with the matting agent of this invention can haveshort curing time, good flexibility, smooth appearance with less orangepeel, and reduced gloss. In addition, matting coating mix having thematting agent of this invention can have desired low viscosity.

This invention is further directed to a method for reducing gloss of adry coating layer on a substrate. The coating layer can be formed from acoating composition. The method can comprise the steps of:

-   -   i) providing a matting agent comprising:        -   a) a silica component;        -   b) a polytrimethylene ether diol having a Mn (number average            molecular weight) in a range of from 500 to 10,000;        -   c) one or more solvents; and        -   d) one or more polymers selected from acrylic polymer,            polyester polymer, or a combination thereof;    -   ii) mixing said matting agent with the coating composition to        form a matt coating mix;    -   iii) applying said matt coating mix over the substrate to form a        wet coating layer; and    -   iv) curing said wet coating layer to form said dry coating        layer.

In one embodiment, the matting agent can consist of:

-   -   a) a silica component,    -   b) a polytrimethylene ether dial having a Mn (number average        molecular weight) in a range of from 500 to 10,000;    -   c) one or more solvents; and    -   d) one or more polymers selected from acrylic polymer, polyester        polymer, or a combination thereof.

In another embodiment, the matting agent can consist essentially of:

-   -   a) a silica component,    -   b) a polytrimethylene ether diol having a Mn (number average        molecular weight) in a range of from 500 to 10,000;    -   c) one or more solvents; and    -   d) one or more polymers selected from acrylic polymer, polyester        polymer, or a combination thereof.

The substrate can include, but not limited to: treated metal; bare metalsuch as blasted steel; aluminum or other metal or alloys; plastic, suchas sheet molded composite (SMC), Reaction Injection Molding (RIM),thermoplastic olefins (TPO) or other resinous materials; glass,concrete, fiberglass, rock, stone or other man-made or nature materials.The substrate can also include consumer electronics such as call phones,TV, digital game devices, telephone set; consumer appliances, such asrefrigerator, washing machine, dishwasher, or microwave set; sportinggoods, such as ski board, bike, and other sport equipments; tools andinstruments, such as hand tools, machines, or other devices; a vehiclebody or vehicle body parts; steel tanks; metal or plastic pipelines;buildings, window frames, guard rails, or other residential orindustrial structures.

The matt coating mix can be applied to the substrate using conventionalcoating application methods, such as spray, rolling, brush, or any othercoating application methods known to those skilled in the art.

The wet coating layer can be cured at ambient or elevated temperaturesto form the dry coating layer. Typically the coating layer can be curedat a temperature in a range of from 18° C. to 60° C. Typically thecoating layer can be cured for a time period, such as in a range of from30 minutes to 24 hours, or any other time period determined necessary bythose skilled in the art.

This invention is further directed to a substrate coated with the mattcoating mix comprising the matting agent.

This invention is even further directed to a substrate coated with theprocess described above.

Testing Procedures

Dry Film Thickness—test method ASTM D4138

Viscosity—can be measured using (1) Zahn Viscosity as determined using a#1 Zahn cup according to ASTM D 1084 Method D; (2) Gardner-Holdt Letterscale according to ASTM D1545; or (3) Brookfield viscometer; asspecified, or in Krebs Unit (KU) viscosity according to ASTM D562-01,respectively, as specified in this invention.

Persoz Hardness Test—the change in film hardness of the coating wasmeasured with respect to time, in second, after application by using aPersoz Hardness Tester Model No. 5854 [ASTM D4366] supplied byByk-Mallinckrodt, Wallingford, Conn.

Molecular weight and hydroxyl number of the polytrimethylene ether diolare determined according to ASTM E222. Molecular weights Mw and Mn andthe polydispersity (Mw/Mn) of the acrylic polymer and other polymers aredetermined by GPC (Gel Permeation Chromatography) using polystyrenestandards and tetrahydrofuran as the solvent.

DOI—Instrumental measurement of distinctness of Image (DOI) gloss ofcoating surfaces is determined according to ASTM D 5767.

Gloss—measured with standard test method for specular gloss according toASTM D 523.

Orange Peel can be tested according to ASTM E284-91 (ACT panel standard.Scores are ranged from 1 to 10 where 1 being high peel and 10 beingsmooth.

EXAMPLES

The present invention is further defined in the following Examples. Itshould be understood that these Examples, while indicating preferredembodiments of the invention, are given by way of illustration only.From the above discussion and these Examples, one skilled in the art canascertain the essential characteristics of this invention, and withoutdeparting from the spirit and scope thereof, can make various changesand modifications of the invention to adapt it to various uses andconditions.

Procedure 1 Preparation of Acrylic Polymers

Acrylic polymers were formed by free-radical copolymerization asdescribed above with monomer ratio as described below. Charge to areactor equipped with a stirrer, reflux condenser and under nitrogen13.7 parts t-butylacetate. Heat to reflux, at approximately 96° C.Premix a monomer mixture of 14.6 parts methyl methacrylate, 5.9 partsstyrene, 11.7 parts hydroxyethyl methacrylate, 14.6 parts n-butylacrylate, 11.7 parts 2-ethylhexyl methacrylate, 1.2 partst-butylacetate. Premix an initiator mixture of 3.4 parts Vazo® 67 (Vazo®67 is available from E.I. DuPont de Nemours and Company, Wilmington,Del., USA, and under respective registered trademark) and 23.2 partst-butylacetate. Feed monomer mixture over 360 minutes at refluxsimultaneously with the initiator mixture. Feed initiator mixture over390 minutes. After the initiator mixture feed was complete, hold 60minutes at reflux. Then cool to room temperature.

The acrylic polymer resin produced herein had the followingcharacteristics: a calculated Tg of +17.6° C., solids 60%, Gardner-Holdtviscosity Y+¼, and weight average molecular weight (Mw) of 10,000.

Procedure 2 Preparation of Linear Polyesters

A linear polyester was prepared by charging the following ingredientsaccording to Table 1 into a reaction vessel equipped with a heatingmantle, water separator, thermometer and stirrer, and under nitrogen.

TABLE 1 Reaction Ingredients (grams). Weight Portion 1 Xylene 19.553Pentaerythritol 93.58 Benzoic acid 167.89 Portion 2. Neopentyl glycol296.21 Isophthalic acid 142.80 Phthallic anhydride 127.29 Adipic acid62.78 Xylene 15.26 Portion 3 Ethyl acetate 113.51

Portion 1 was added to the reactor and heated to its reflux temperature,about 190° C. The reactor was heated stepwise to 215° C. and held untilthe acid number was 33 or less. After cooling the reactor to 80° C.,Portion 2 was added and the reactor was heated to reflux, about 175° C.The temperature was then increased stepwise to 215° C. That temperaturewas held until an acid number between 3 and 7 at about 98 wt % solidswas reached. Portion 3 was added after cooling to about 80° C. Theresulting polymer had a wt % solids of about 82%, and Gardner-Holdtviscosity between Z1+½ to Z3+¼. The linear polyester has a weightmolecular weight of Mw 1,700, and a Tg of +3° C.

Comparative Matting Agent Compositions

Comparative compositions were prepared according to Table 2. Theingredients were added in the order of solvent, acrylic polymer orpolyester, silica while mixing in a can with a air mixer for 30 minutes.Comparative Examples 1, 2, 5 and 7 had silica flocculation and were toothick to measure viscosity.

TABLE 2 Matting Agent Composition (parts in weight). Com 1 Com 2 Com 3Com 4 Com 5 Com 6 Com 7 Com 8 Organic Silica ⁽¹⁾ 10 — 10 — 10 — 10 —Fumed silica ⁽²⁾ — 10 — 10 — 10 — 10 Polytrimethylene — — — — — — — —ether diol ⁽³⁾ Terethane ⁽⁴⁾ 5 5 — — — — — — PPG2000 ⁽⁵⁾ — — 5 5 — — — —Simms Diol ⁽⁶⁾ — — — — 5 5 CAPA 2100A ⁽⁷⁾ — — — — 5 5 Acrylic Polymer⁽⁸⁾ 15 15 15 15 15 15 15 15 Polyester ⁽⁹⁾ — — — — — — — — Solvent ⁽¹⁰⁾70 70 70 70 70 70 70 70 Total 100 100 100 100 100 100 100 100 Viscosityof the Too Too 80 80 Too N/A⁽¹¹⁾ Too N/A⁽¹¹⁾ Matting Agent thick thickthick thick (KU) Com 9 Com 10 Com 11 Com 12 Com 13 Organic Silica ⁽¹⁾ 10— 10 — 10 Fumed silica ⁽²⁾ — 10 — 10 — Polytrimethylene — — — — — etherdiol ⁽³⁾ Terathane ⁽⁴⁾ — — — — — PPG2000 ⁽⁵⁾ — — — — — Simms Diol ⁽⁶⁾ —— — — — CAPA 2100A ⁽⁷⁾ — — — — — Acrylic polymer ⁽⁸⁾ 20 20 — — 20Polyester ⁽⁹⁾ — — 20 20 — Solvent ⁽¹⁰⁾ 70 70 70 70 70 Total 100 100 100100 100 Viscosity of the 75 75 75 75 75 Matting Agent (KU) ⁽¹⁾ OrganicSilica OK412: available as ACEMATT ® OK 412 from Evonik Industries AG,Essen, Germany under respective registered trademark. ⁽²⁾ Fumed silicaTS-100: available as ACEMATT ® TS 100 from Evonik Industries AG, Essen,Germany under respective registered trademark. ⁽³⁾ Polytrimethyleneether diols were prepared according to the process described in U.S.Pat. No. 6,875,514, col. 9, line 29 through col. 10, line 8.Characteristics of the polytrimethylene ether diols include: numberaverage molecular weight (Mn) was about 1,300-1,450, hydroxyl number of77.4-86.3 and a glass transition temperature (Tg) of about −75° C. ⁽⁴⁾Terathane ® is a polyether glycol available from Invista, Wichita, KS,USA, under the respective registered trademark. ⁽⁵⁾ PPG2000:polypropylene glycol having a molecular weight of 2000 from AldrichChemical Company, Product No. 81380. ⁽⁶⁾ Simms Diol is a hydroxyloligomer of the reaction product of 3 moles of carprolactone and 1 moleof 1,4-cyclohexane dimethanol as disclosed in U.S. Pat. No. 7,169,475.⁽⁷⁾ Polyester diol CAPA ® 2100A is available from Perstorp SpecialtyChemicals AB, Sweden, under respective registered trademark. ⁽⁸⁾ Acrylicpolymer was prepared according to Procedure 1. ⁽⁹⁾ Polyester wasprepared according to Procedure 2. ⁽¹⁰⁾ Oxsol ® 100 is a solventavailable from MANA, New York, NY, USA, under respective registeredtrademark. ⁽¹¹⁾ Not assayed or data not available.

Matting Agent Examples

Matting agent examples according to this invention were preparedaccording to Table 3.

TABLE 3 Matting Agent Composition (parts in weight). Exp 1 Exp 2 Exp 3Exp 4 Exp 5 Organic Silica ⁽¹⁾ 10 — 10 — 10 Fumed silica ⁽²⁾ — 10 — 10 —Polytrimethylene 5 5 5 5 5 ether diol ⁽³⁾ Terathane ⁽⁴⁾ — — — — —PPG2000 ⁽⁵⁾ — — — — — Simms Diol ⁽⁶⁾ — — — — — CAPA 2100A ⁽⁷⁾ — — — — —Acrylic polyol ⁽⁸⁾ 15 15 — — 15 Polyester polyol ⁽⁹⁾ — — 15 15 — Solvent⁽¹⁰⁾ 70 70 70 70 70 Total 100 100 100 100 100 Viscosity of the 70 70 7070 70 Matting Agent (KU) Footnote: Same as Table 1.

Coating Property

Imron® Industrial Strength™ Polyurethane 9T01 is a 2K coatingcomposition available from E.I. DuPont de Nemours and Company,Wilmington, Del., USA, under respective registered or unregisteredtrademarks. Activated coating mix was activated according tomanufacturer's instruction. Each of the matting agents prepared abovewere mixed with the activated coating mix to form a matt coating mix.The mixing ratio was 1:1 in volume, i.e., one volume of the mattingagent was mixed with one volume of the activated coating mix.

The Comparative matting agents Corn 1, 2, 5, 6, 7 and 8 were too thickfor any practical use. No coating property data were obtained from thosecomparative compositions.

Each of the matt coating mix was applied by U-shaped bar (4-milclearance, available as Cat. No. PA-5305, from BYK Gardner, Columbia,Md. USA, over a cold roll steel, available as APR10433, B-1000 P60 DIWUnpolished, from ACT Test Panels LLC, Hillsdale, Mich., USA.

The coatings were allowed to cure for 24 hours (or as indicatedotherwise) at ambient temperature. Coating properties were measured atindicated time points according to Testing Procedures described above.

Data in Table 4 show that the matting agent of this invention providedexcellent coating property in combination of low viscosity, shortercuring time, reduction in gloss, higher flexibility, and desiredappearance.

TABLE 4 2K Coating Properties. Com 1 Com 2 Com 3 Com 4 Com 5 Com 6 Com 7Com 8 Viscosity of Matt N/A N/A 70 70 N/A N/A N/A N/A Coating Mix (KU)Gloss at 60 N/A N/A 75 70 N/A N/A N/A N/A Degree Cure Time N/A N/A >48hr >48 Hr N/A N/A N/A N/A Appearance N/A N/A No Many N/A N/A N/A N/Aseeds Seeds Orange Peel N/A N/A N/A N/A N/A N/A N/A N/A Flexibility N/AN/A N/A N/A N/A N/A N/A N/A Persoz Hardness N/A N/A N/A N/A N/A N/A N/AN/A Com 9 Com 10 Com 11 Com 12 Exp 1 Exp 2 Exp 3 Exp 4 Viscosity of Matt65 65 70 70 60 60 60 60 Coating Mix (KU) Gloss at 60 10 30 20 40 10 3010 30 Degree Some Some Seeds Seeds Cure Time 2 hr 2 hr 2 hr 2 hr 2 hr 2hr 2 hr 2 hr Appearance Some Many Some Many Good Many Good Many SeedsSeeds Seeds Seeds Seeds Seeds Orange Peel 1 N/A  1 N/A  5 N/A  5 N/AFlexibility  15%  15%  15%  15%  28%  28%  28%  28% Persoz Hardness 8070 70 60 80 70 80 70 Note: The Comparative matting agents Com 1, 2, 5,6, 7 and 8 were too thick for any practical use. No coating propertydata were obtained from those comparative compositions. Some coatingproperties were not measured for Com 3 and 4.

Tufcote® 3.5 HG-D™ is a high gloss 1K coating available from E.I. DuPontde Nemours and Company, Wilmington, Del., USA, under respectiveregistered or unregistered trademarks. Gloss reading of the Tufcote® 3.5HG-D™ is about 90 without any matting agent according to manufacturer'sdata. Each of the matting agents Corn 13 and Exp 5 prepared above wasmixed with the Tufcote® 3.5 HG-D™ to form a matt coating mix. The mixingratio was 1:1 in volume, i.e., one volume of the matting agent was mixedwith one volume of the Tufcote® 3.5 HG-D™.

The matting coating mix was each applied to a substrate and cured asdescribed above. Coating properties were measured and shown in Table 5.

TABLE 5 1K Coating Properties. Com 13 Exp 5 Viscosity of Matt CoatingMix (KU) 58 55 Gloss at 60 Degree 10 8 (Some seeds) Cure Time 2 hours 2hours Appearance Some Seeds No Seeds Orange Peel 2 6 Flexibility 15% 28%Persoz Hardness 78 75

What is claimed is:
 1. A matting agent consisting essentially of: a) asilica component, b) a polytrimethylene ether diol having a Mn (numberaverage molecular weight) in a range of from 500 to 10,000; c) one ormore solvents; and d) one or more polymers, wherein said one or morepolymers are acrylic polymers, polyester polymers, or a combinationthereof; wherein said silica component comprises silica particles havingan average particle size in a range of from 2 to 20 micrometers and saidsilica particles are hydrophobic silica particles.
 2. The matting agentof claim 1, wherein the polytrimethylene ether diol has a Mn in a rangeof from 500 to 4,000, a Tg of about −75° C. and a hydroxyl number in arange of from 20 to
 200. 3. The matting agent of claim 1, wherein thepolytrimethylene ether diol is a blend of high and low molecular weightpolytrimethylene ether diols wherein the high molecular weightpolytrimethylene ether diol has an Mn in a range of from 1,000 to 4,000and the low molecular weight polytrimethylene ether diol has an Mn in arange of from 150 to 500 and the average Mn of the blend is in a rangeof from 1,000 to 4,000.
 4. The matting agent of claim 1, wherein thepolytrimethylene ether diol is polymerized from bio-derived1,3-propanediol.
 5. The matting agent of claim 1, wherein said acrylicpolymers are selected from linear or branched acrylic polymer having oneor more hydroxyl functional groups, or a combination thereof.
 6. Thematting agent of claim 1, wherein said polyester polymers are selectedfrom linear or branched polyester polymer having one or more hydroxylfunctional groups, or a combination thereof.
 7. A method for reducinggloss of a dry coating layer on a substrate, said coating layer isformed from a coating composition, said method comprising the steps of:i) providing a matting agent consisting essentially of: a) a silicacomponent; b) a polytrimethylene ether diol having a Mn (number averagemolecular weight) in a range of from 500 to 10,000; c) one or moresolvents; and d) one or more polymers selected from acrylic polymer,polyester polymer, or a combination thereof, wherein said silicacomponent comprises silica particles having an average particle size ina range of from 2 to 20 micrometers and said silica particles arehydrophobic silica particles; ii) mixing said matting agent with saidcoating composition to form a matt coating mix; iii) applying said mattcoating mix over said substrate to form a wet coating layer; and iv)curing said wet coating layer to form said dry coating layer.
 8. Themethod of claim 7, wherein said coating composition comprises acrosslinakble component and a crosslinking component.
 9. The method ofclaim 8, wherein said crosslinkable component comprises hydroxylcrosslinkable functional groups.
 10. The method of claim 8, wherein saidcrosslinking component comprises isocyanate crosslinking functionalgroups.
 11. The method of claim 7, wherein said coating composition isselected from a one-pack coating composition or a two-pack coatingcomposition.
 12. The method of claim 7, wherein said substrate is tools,equipments, sporting goods, vehicle body, vehicle body parts, consumerelectronics, consumer appliances, residential or industrial structures.13. A substrate coated with the method of claim
 7. 14. A substratecoated with a matt coating mix comprising the matting agent of claim 1and a coating composition.